Ethylenic sulfilimine compositions for controlling fungi, bacteria and algae

ABSTRACT

The use of selectively oxidized ethylenic sulfilimines of the formula TO PROTECT AGRICULTURAL, ORGANIC, AND RELATED ARTICLES FROM ATTACK BY NOXIOUS LIVING ORGANISMS, SUCH AS FUNGI, BACTERIA AND ALGAE.

United States Patent [151 3,653,873

Bayer [45] Apr. 4, 1972 541 ETHYLENIC SULFILIMINE 2,075,359 6/1937Salzberg et a1 ..424/250 COMPOSITIONS FOR CONTROLLING P Ex Lewis Gemrzmary ammer- FUNGI BACTERIA AND ALGAE Assistant ExaminerCatherine L.Mills [72] I ve t r; H t o,B ,L in P Attorney-George W. F. Simmons, CarlA. Castellan and Arthur R. Eglington [73] Assignee: Rohm and HaasCompany, Philadelphia,

57 ABSTRACT Filed: 1970 The use of selectively oxidized ethylenicsulfilimines of the 21 Appl. No.: 12,149 fmmula Related U.S. ApplicationData H H [62] Division of Ser. No. 705,916, Feb. 16, 1968, Pat. No. R,=C

3,542,865. OzSN=SR sonR' 52 u.s.c| ..7l/67,7l/l03,424/32l [5i] Int.Cl...A0ln9/16 [58] Field ofSearch ..71/67;424/321 I to protectagricultural, organic and related articles from [56] References Citedattack by noxious living organisms, such as fungi, bacteria and al ae.UNITED STATES PATENTS g 9 Claims, No Drawings 1,9 1 5 3 314 6[i 9 33 V Salzb e rg e t al.. ,....26O/243 E'I'HYLENIC SULFILIMINE COMPOSITIONS FORCONTROLLING FUNGI, BACTERIA AND ALGAE This application is a divisionalof 0.8. Ser. No. 705,916, filed Feb. 16, 1968 now U.S. Pat. No.3,542,865.

This invention relates to novel selectively oxidized ethylenicsulfimines, to methods for their preparation, and to agriculturalcompositions containing them as the active ingredient. Moreparticularly, this invention relates to novel biocidally activecompositions comprising ethylenic sulfilimines characterized by eitherhydrocarbylsulfmyl or hydrocarbylsulfonyl ethylenic substitution whichis hereinafter defined. The novel compounds are used to protectagricultural, organic and related articles, such as textiles, paints,plastics and detergents from attack by noxious living organisms, such asfungi, bacteria and algae.

Although there are literature reviews, such as F. Challenger, OrganicSulfur Compounds, Vol. I, Pergamon Press, New York, N. Y., 1961, pp.339-349 relating to the production of sulfilimines by condensationreactions involving various sulfides with sodiumtoluene-p-sulfonchloroamide, referred to hereinafter as chloroamine-T,there has not been even a remote suggestion of the compounds of thisinvention. Sulfilimines have been prepared generally by reacting anaqueous solution of chloroamine-T with a solvent solution of ahalogen-containing sulfide, such as Lbromoethylethylsulfide to produce aquadrivalent sulfur compound. Additionally,

chloroamine-T has been reacted with RSC I-LSR', RSCH CHSR and RS(CH),,SR.

In accordance with this invention novel biocidally active selectivelyoxidized ethylenic sulfilimines are produced in a reaction process whichcomprises reacting chloroamine-T with a cisor trans-1,2-bis(hydrocarbylthio)ethylene to form a condensation productcontaining a quadrivalent sulfur atom, and then selectively reacting thecondensation product with an oxidizing agent under controlled conditionsto produce either cisor trans-l-(hydrocarbylthio-S-tolylsulfonylimino)-Z-(hydrocarbylsulfinyl and hydrocarbylsulfonyl)ethylenes, or a mixturethereof.

The compounds of this invention can exist as either the cis or the transisomer. The following is a generic formula for the compounds of thisinvention; although it is represented as a cis isomer, it is alsointended to cover the corresponding trans isomer:

where n is an integer from 1 to 2 inclusive; x is or the integer l; Rand Rare hydrocarbyl radicals and may be the same or different, and areselected from aryl groups, such as phenyl, etc., halophenyl such asp-chlorophenyl, p-fluorophenyl, etc., alkoxyaryl groups such asmethoxyphenyl, etc., alkaryl groups such as tolyl, etc., aralkyl groupssuch as benzyl, phenethyl, etc., halobenzyl such as p-chlorobenzyl,p-fluorobenzyl, etc., alkoxybenzyl such as methoxybenzyl, etc.; R isselected from hydrogen, C -C alkyl and halogen.

lt has been discovered that the selectively oxidized sulfilimines ofthis invention are more active than their nonoxidized analogs incontrolling the growth and propagation of noxious living organisms, suchas fungi, bacteria and algae.

Suitable oxidizing agents that may be used in this invention are thosecapable of oxidizing sulfides such as hydrogen peroxide, organicper-acids such as m-chloroperbenzoic acid, peracetic acid, performicacid, perbenzoic acid; potassium permanganate, sodium hypochlorite,chromic oxide, dilute nitric acid, etc. There is no general scheme forselectively oxidizing the sulfilimines (n=0) because the sulfiliminegroup won t survive certain conditions of temperature and pH. In theexamples described hereinbelow m-chloroperbenzoic and hydrogen peroxidewere used to selectively oxidize the corresponding l ,2-bis(hydrocarbylthio)-S-tolylsulfonyliminoethylene. The oxidation reactionconditions will vary with the particular oxidizing agents used.

Suitable solvents that can be used, if desired, as the oxidationreaction medium are hydrocarbons, such as benzene, heptane, petroleumether, toluene or the like, chlorinated hydrocarbons, such as carbontetrachloride, methylene chloride, ethylene chloride, chlorobenzene orthe like, alcohols, such as ethanol, ketones such as acetone, esterssuch as ethyl acetate, or an excess of one or the other reactant orproduct serving as solvent.

Representative compounds within the generic structure of this inventionare cis-1-(phenylsulfinyl)-2-(phenylthio-S- tosylimino )ethylene, cislphenylthio-Stosylimino )-2- (phenylsulfonyl)ethylene, translphenylthio-S-tosylimino 2-( phenylsulfmyl)ethylene, trans-1phenylthio-S- tosylimino )-2-(phenylsulfonyl)ethylene, cislp-tolylthio-S- 2-( benzylthio-S-tosylimino)ethylene, cisl benzylthio-S-tosylimino)-2-(benzylsulfonyl)ethylene, transl -(benzylsulfinyl )-2-(benzylthio s-tosylimino )ethylene trans- 1 benzylthio-S-tosylimino )-2-(benzylsulfonyl)ethylene, cisl (p-methoxybenzylthio-S-tosylimino)-Z-(p-methoxybenzylsulfinyl)ethylene,cis-1-(p-fluorophenylsulfinyl)-2-(p-methoxybenzylsulfinyl)ethylene,cis-l-(p-fluorophenylsulfinyl)-2-(pfluorophenylthio-S-tosylimino)ethylene,cislp-fluorophenylthio-S-tosylimino)-2-(p-fluorophenylsulfonyl)ethylene,cis- 1-(p-chlorophenylsulfinyl)-2-(p-chlorophenylthio-S-tosylimino)ethylene,cis-l-(p-methoxyphenylsulfinyl)-2-(pmethoxyphenylthio-S-tosylimino)ethylene,cislp-methoxyphenylthio-S-tosylimino)-2-(p-methoxyphenylsulfonyl)ethylene.The term tosyl" asused herein represents the p-tolylsulfonyl radical.

To assist those skilled in the art to practice the present invention,the following procedures are suggested by way of illustration, parts andpercentages being by weight unless otherwise specifically noted.

]. Trans-l ,2-bis( phenylthio )-S-tolylsulfonyliminoethylene To 24.0 g.[0.0985 mole] of trans-l,2-bis(phenylthio)ethylene in 200 ml. ofdimethylformamide was added 56.0 g. [0.199 mole] of chloroamine-T. Themixture was stirred for about 24 hours at room temperature, and thenpoured into one liter of iced water. The chilling caused the separationof a thick, colorless oil. The aqueous layer was decanted and the oilwas stirred into methanol. After standing for several hours at roomtemperature, a colorless solid formed which was collected by filtrationand dried to provide 34.2 g. (83 percent yield) oftrans-l,2-bis(phenylthio)-S-tolylsulfonyliminoethylene having a meltingpoint of 89-90 C.

Anal. Calculated for c,,H,,No,s,:

Theoretical: C, 60.99; H, 4.63; N, 3.39; S, 23.26.

Found: C, 60.90; H, 4.51; N, 3.48; S, 22.92.

The ethylenic sulfilimine intermediate produced in Procedure 1 was thenselectively oxidized, as in Procedures 2 and 3 to produce compounds ofthis invention.

2. Trans-l (phenylthio-S-tolylsulfonylimino)-2- (phenylsulfinyl)ethyleneTo 15.0 g. [0.0364 mole] of trans-l,2-bis(phenylthio)-S-tolylsulfonyliminoethylene dissolved in 100 ml. of chloroform at 0 C.was added 7.5 g. [0.037 mole] of 85 percent mchloroperbenzoic acid. Themixture was stirred for one-half hour at 0 C. The mixture was thenpermitted to stand at room temperature. After about one hour the mixturewas again cooled to 0 C. The insoluble m-chlorobenzoic acid wasseparated by filtration. The filtrate was stripped and the concentratewas mixed with 75 ml. of methanol. On standing, a colorless solid formedwhich was separated by filtration and recrystallized from methanolgiving 12.5 g. percent yield) oftrans-l-(phenylthio-S-tolylsulfonylimino)-2-(phenylsulfinyl)ethylenehaving a melting point of l58-l 60 C.

Anal. Calculated for c,,H,,,No,s,;

Theoretical: C, 58.72; H, 4.46; N, 3.26; S, 22.39.

3. Trans- 1 phenylthio-S-tolylsulfonylimino )-2- (phenylsulfonyl)ethylene To 4.0 g. [0.00933 mole] oftrans-l-(phenylthio-S-tolylsulfonylimino)-2-(phenylsulfinyl)ethylenedissolved in 25 ml. of chloroform was slowly added 2.5 g. [0.0121 mole]of 85 percent m-chloroperbenzoic acid at about 10 C. When addition wascompleted, the mixture was stirred for one-half hour and then cooled inan ice bath. The insoluble m-chlorobenzoic acid was separated byfiltration. The filtrate was stripped and the concentrate was taken upin hot methanol. The concentrate solution was then cooled to form acolorless solid which was filtered and dried to provide 3.0 g. (72percent yield), oftrans-l-(phenylthio-S-tolylsulfonylimino)-2-(phenylsulfonyl)ethylenehaving a melting point of 140l42 C.

Anal. Calculated for C l-l NOfi Theoretical: C, 56.61; H, 4.30; N, 3.14;S, 21.59.

Found: C, 56.84; H, 4.18; N, 3.05; S, 21.60.

The preparation of cis-l ,2-bis( p-tolylthio)-S-tolylsu1-fonyliminoethylene which is used as a starting material in Procedures 4and 5 is described by Leandri et al., Ann. Chem. Rome, 50, 1616-26(1960).

4. Cis-l-(p-tolylthio-S-tolylsulfonylimino)-2-(ptolylsulfinyl)ethyleneTo 5.0 g. [0.0113 mole] ofcis-l,2-bis(p-tolylthio)-S-tolylsulfonyliminoethylene in 50 ml. ofchloroform at C. was slowly added 2.44 g. [0.0119 mole] of 85 percentmchloroperbenzoic acid. The mixture was allowed to stand for 1 hour atroom temperature. The reaction mixture was then tolylsulfonyl)ethylenehaving a melting point of l37-l 39 C sodium sulfate and stripped toproduce a gum-like concentrate. The concentrate was taken up in 25 ml.of hot methanol. The solution was then cooled to form a colorlessprecipitate which was filtered and dried to provide 3.3 g. (64 percentyield) of cisl-(p-tolylthio-S-tolylsulfonylimino)-2-(p-tolylsulfinyl)ethylene having amelting point of 14 l -l42 C.

Anal. Calculated for c n uqs Theoretical: C, 60.36; H, 5.06; N, 3.06; S,21.02.

Found: C, 60.37; H, 5.27; N, 2.81; S, 20.94.

5. Cis-l-( p-tolylthio-S-tolylsulfonylimino)-2-(ptolylsulfonyl )ethyleneTo 7.0 g. [0.0158 mole] ofcis-l,2-bis(p-tolylthio)-S-tolylsulfonyliminoethylene in 20 ml. ofglacial acetic acid was added 7.0 m1. of percent hydrogen peroxide. Themixture was heated to about C. and held at this temperature for 1 hour.The reaction mixture was cooled and poured into 100 ml. of iced water. Asolid formed and was separated by filtration and recrystallized frommethanol to provide 5.5 g. (73 percent yield) ofcis-l-(p-tolylthio-S-tolylsulfonylimino)-2-(p- Anal. Calculated for Cl-l NO S Theoretical: C, 58.33; H, 4.89; N, 2.95; S, 20.31.

Found: C, 58.26; H, 4.88; N, 2.91; S, 20.22.

The following Tables A and B list compounds that were prepared inaccordance with the methods described in Procedures 2 and 3respectively. The compounds listed conform to the formula CH C H SO,NS(R)Cl-l E CHSO,,R' where R and R represent, in this instance, the sameradical. In the elemental analysis portion of the table, T representstheoretical and F represents found.

TABLE A Carbon Hydrogen Nitrogen Sulfur Halogen Percent Rand R 'n.Isomer yield M.P. T F T F T F T F T F F@ 1 Cis 23 -72 54.18 54.50 3.683.81 3.01 3.13 20.66 20.92 8.16 9.85

CH3O 1 do. 53 -17 55.42 56.44 4.73 4.64 2.86 3.02 19.65 19.58

CH. 1 .d0 61 153-5 60.37 60.40 5.07 5.00 3.61 3.68 21.02 20.58

CH2 1 Trans 44 152-4 60.37 60.80 5.07 5.18 3.61 3.25 21.02 20.57

TABLE B Carbon Hydrogen Nitrogen Sulfur Halogen Percent Rand R n Isomeryield M.P. T F T F T F T F T F F@ 2 C15 84 126-30 52.38 52.48 3.55 3.662.90 3.18 19.98 20.10

c1@ 2 do-- 40 -6 49.03 49.03 3.31 3.29 2.73 2.81 18.70 17.72 13.7813.79-

OH10 2 .do.. 59 121-3 54.63 54.60 4.59 4.51 2.77 281 19.03 19.31

H: 2 do-.-.. 75 149-8 58.33 58.46 4.89 5.12 2.95 3.20 20.31 20.18

Q-flh 2 Trans. 61 151-3 58.33 58.46 4.89 5.00 2.95 2.91 20.31 20.08

cooled to about 5 C. The insoluble m-chlorobenzoic acid was then removedby filtration. The filtrate was extractedwith 10 percent sodiumhydroxide solution, then dried over anhydrous 75 To illustrate theirbroad spectrum of biological activity, compounds of this invention werebioassayed in standard fungicide, bactericide, and algicide tests.Specifically, fungicidal activity was determined in standard fungicidaltests against Piricularia oryzae Cav., Helminlhosporium oryzae,Alrernaria solani, Botrytisfabae and Erysiphe polygoni. Fungicidalactivity was also determined in streak tests and serial dilution testsagainst Aspergillus niger, Rhizopus sp. and Rhodotorula sp. Bactericidalactivity was determined in streak tests and serial dilution testsagainst Escherichia coli and Staphylococcus aureus, and in additionalstreak tests against Pseudomonas aeruginosa. Algicidal activity wasdetermined in streak tests against Chlorella pyrenoidosa, Square D algaeand Scenedesmus abliquus, and in serial dilution tests against Chlorellapyrenoidosa and Pharmidium inundatum. The results of the variousbiocidal evaluation tests are given in tabular form following thedescription of the test method. In the tables, the active ingredients(A1.) are represented by the letters A to O which are respectively:

(chlorophenylsulfinyl )ethylene TOMATO EARLY BLIGHT Biocidal evaluationtests were conducted in which ethylenic sulfilimines having onlyhydrocarbylthio ethylenic substitution (n=) were compared with compoundsrepresentative of this invention in their ability to control the tomatoearly blight disease. Early blight is one of the most importantdefoliating diseases of the tomato. In the early blight control test,tomato plants at the four-leaf stage were sprayed to run-off withsuspensions containing 1,200 p.p.m. of the compounds under evaluation.The sprayed plants were then allowed to dry. The plants were thenweathered in a fog chamber for about 18 hours. They were then stored inthe greenhouse at room temperature for about 24 hours. The plants werethen inoculated with a suspension of 25,000 30,000 spores per ml. ofAlternaria solani. The spores were incubated by holding the inoculatedplants at about 52 F. and 100 percent relative humidity for about 22hours. The plants were then placed in an illuminated test room and heldat about 75 F. for a period of 4 days.The disease lesions that developedon the plants were then counted after the 4-day residence period in theilluminated test room. Each compound was then assigned an activityrating based on the lesion count. The activity ratings ranged from notactive to very active. A rating of not active indicated that the numberof disease lesions counted were about the same as the number of diseaselesions counted on an untreated plant. The results of the tests aregiven in Table I. In the table and hereinafter, the term Al.

represents the active ingredient in the suspension used to spray thecrop plant prior to its inoculation with the noxious organism; theoxidation levels of each test compound are represented by I" when n=0,ll when n=l and "1" when n=2.

TABLE I Control of Tomato Early Blight A.i. l n m A ivct Active B Activec I Very Active D No! Active E Active F Very Active CONTROL OF RICEBLAST Tests to determine the ability of the compounds of this inventionto control the disease of rice blast were conducted in the same manneras the persistency-type tests for the control of tomato early blight,except about 40,000 spores of Piricularia oryzae were substituted as thenoxious organisms. The

CONTROL OF RICE HELMINTHOSPORIUM The compounds of this invention wereevaluated in rice helminthosporium control tests. The tests wereconducted in the same manner as the tests associated with Table 1,except the spray treated plants were not subjected to weathering afterdrying. In addition, about 40,000 spores of Helminthosporium oryzae weresubstituted as the noxious organisms. The results of the tests are givenin Table III.

TABLE III Control of Rice Helminthosporium A1. I II A Not Active VeryActive CONTROL OF BOTRYTIS ON FABA BEAN Tests were conducted in the sameway as the tests for the control of rice helminthosporium, except100,000 spores of Botrytis cinerca were substituted as the noxiousorganisms. The results of the tests are given in Table IV.

' ranging from about 1,000 p.p.m. to about 0.5 p.p.m. The

TABLE IV A.I. I II III A Not Active B Very Active C Very Active D I NotActive E Active F Very Active In addition to the fungicidal testsdescribed hereinabove, the antimicrobial activities of the ethylenicsulfilimines of this invention were evaluated against representativealgae and bacteria in streak tests and in serial dilution tests.

SERIAL DILUTION TESTS In the serial dilution tests, two-fold serialdilutions of the toxicant in the test medium were prepared in a dosageseries medium used for the tests against bacteria was Trypticase soybroth, and the medium used in the tests against algae was Allens liquidmedium. The test media were inoculated with the disease organisms. Theinoculated media were then incubated. The test series was then inspectedto determine the minimum amount of toxicant required to inhibit thegrowth of the noxious organisms. The minimum concentration of toxicantwas then reported as either the minimum algaestatic concentration,referred to in Table V as MAC" or the minimum bacteriostaticconcentration, referred to in Table V as MBC.

In the serial dilution tests against algae the noxious organisms wereChlorella pyrenoidosa (Chlor.) and Phormidium inundatum (Phor.). Afterinoculation with the noxious organisms, the treated media were incubatedfor 7 days on a culture shaker at room temperature under continuousfluorescent light. The minimum microbistatic concentration was thenbased on the minimum concentration which inhibited growth.

In the serial dilution tests against bacteria the disease organisms wereEscherichia coli (Esch.) and Staphylococcus aureus (Staph). Afterinoculation with the noxious organisms, the treated media were incubatedfor 48 hours at 37 C. The results of the serial dilution tests are givenin Table V. The symbols used in the table are defined hereinabove.

TABLE V Serial Dilution Tests A.l c111. Phor. Staph. Each.

1; 2.0 1.0 0: 1.000 c 1.0 0.5 :11 500 F 1.0 0.25 11 1.0 05 51 500 1 0.50.25 1. 31 1.000 M 5.0 0.5 N 0.5 0.5 o 1.0 0.25

STREAK TESTS In the streak tests the test compounds were incorporated ina liquid agar at two concentrations namely at 10 p.p.m. in the testagainst algae and 1,000 p.p.m. in the tests against bacteria. The agarwas then solidified and the disease producing organisms were streakedonto the solid surface of the agar. In the streak tests against algaethe noxious organisms were Scenedesmus obliquus (Scen.), Square D algae(S.D.) and Chlorella pyrenoidosa (Chlor.). In the streak tests againstbacteria the disease organisms were Pseudomonasaeruginosa (P- seud.),Escherichia coli (Esch.) and Staphylococcus aureus (Staph). The mediumused in the streak tests against algae was Allens agar, and the mediumused in the streak tests against bacteria was Tryptone glucose extractagar. After infection with the disease organisms, the treated agars werethen incubated. The incubation periods for the algicidal and bactericidal streak tests were respectively 5 days at room temperatureunder fluorescent light, and 48 hours at 37 C. After the incubationperiod, the activity of the toxicant was evaluated on a rating scale offrom 0 to 4 where 0 indicates complete inhibition of growth andexcellent activity, 1 indicates considerable inhibition of growth andgood activity, 2 indicates slight growth and moderate activity, 3indicates slight inhibition of growth and 4 indicates a heavy growthequivalent to an untreated control and no activity. The results of thestreak tests are given in Table VI. The symbols used in the table aredefined hereinabove.

The compounds of this invention are useful as broad spectrum fungicides.They can be applied to plants or other areas to be protected bycontacting such area with a compound of this invention contained in aformulation that is suitable for dissemination as a fungicide. Incertain operations, the unmodified compounds are distributed orincorporated in pesticidal amounts in adhesives, soaps, inks, plasterwallboard, cutting oils, textiles, paper, polymeric materials, paints,embalming fluids, lumber, wood products or growth media, below theground or upon the surfaces of the above-ground portion of plants toprevent the attack of various fungal pests and the subsequent economicloss due to the degradation of such products by microorganisms. However,the present method also embraces the employment of liquid or dustcompositions containing the toxicants. When the compounds of thisinvention are used as fungicides, they may be formulated as finelydivided, wettable powders, dusts and granular materials, solutions,concentrates, emulsifiable concentrates, slurries, and the like,depending upon the particular application intended and the formulationmedia desired. In such usage, the compounds are modified with one or aplurality of additaments of adjuvants including water, organic solvents,petroleum oils, petroleum distillates, naphthas, or other liquidcarriers, polymeric thickening agents, urea, surface-active dispersingagents and finely divided inert solids. When liquid formulations areemployed, or dry materials prepared which are to be used in liquid form,it is desireable, in certain instances, additionally to employ awetting, emulsifying or dispersing agent to facilitate use of theformulation. Suitable surfactants are disclosed by J. W. McCutcheon inSoap and Chemical Specialties, Vol. 31, Nos. 7 to 10 (1955). The exactconcentration of the toxicants to be employed in the treatingcompositions is not critical and may vary considerably provided therequired dosage of the efiective agent is supplied to the area to betreated. The concentration of toxicant in liquid compositions generallyis from about 0.0001 to 50 percent by weight. Concentrations up to 95percent by weight are oftentimes conveniently employed. In dusts, theconcentrations of the toxicant can be from about 0.1 to 95 percent byweight. In compositions to be employed as concentrates, the toxicantscan be present in a concentration of from to 98 percent by weight. Thequantity of treating composition to be applied to textiles, lumber orgrowth media or to the foliage of plants may vary considerably providedthat the required dosage of active ingredients is applied in sufficientamounts of the finished composition adequately to cover the vegetationto be treated or to facilitate the penetration and distribution of saidingredients in and on textiles, lumber or growth media.

In the preparation of dust compositions, the toxicant products can becompounded with any of the finely divided solids, such as pyrophyllite,talc, chalk, gypsum, and the like. In such operations, the finelydivided carrier is ground or mixed with the toxicant or wet with asolution of the toxicant in a volatile organic solvent. Similarly, dustcompositions containing the products can be compounded with varioussolid surface-active dispersing agents such as fullers earth, bentonite,attapulgite and other clays. Depending upon the proportions ofingredients, these dust compositions can be employed for the control ofpests or employed as concentrates and subsequently diluted with anadditional solid surface-active dispersing agent or with pyrophyllite,chalk, talc, gypsum and the like to obtain the desired amount of activeingredient in a composition adapted to be employed for the control offungi. Also, such dust compositions when employed as concentrates can bedispersed in water, with or without the aid of dispersing agents to formspray mixtures.

Further, spray compositions can be prepared by incorporating thetoxicants of this invention or their liquid or dust concentratecompositions in intimate mixtures with surface-active dispersing agentssuch as an ionic or non-ionic emulsifying agent. Such compositions arereadily employed for the control of pests or are dispersed in liquidcarriers to form diluted sprays containing the toxicants in any desiredamount. The choice of dispersing agents and amounts thereof employed aredetermined by the ability of the agents to facilitate the dispersion ofthe concentrate in the liquid carrier to produce the desired spraycompositions.

Similarly, the toxicant products can be compounded with a suitablewater-immiscible organic liquid and a surface-active dispersing agent toproduce an emulsifiable concentrate which can be further diluted withwater and oil to form spray mixtures in the form of oil-in-wateremulsions. In such compositions, the carrier comprises an aqueousemulsion, i.e., a mixture of water-immiscible solvent, emulsifying agentand water. Preferred dispersing agents which can be employed in thesecompositions are oil-soluble and include the non-ionic emul- Sifterssuch as polyoxyethylene derivatives or sorbitan esters, complex etheralcohols and the like. Also, oil-soluble ionic emulsifying agents suchas mahogany soaps can be used. Suitable organic liquids which can beemployed in the composition include petroleum oils and distillates,toluene, liquid halohydrocarbon and synthetic organic oils. Thesurface-active dispersing agents are usually employed in liquidcompositions in the amount of from 0.1 to 20 percent by weight of thecombined weight of the dispersing agent and active compound.

In addition, other liquid compositions containing the desired amount ofeffective agent can be prepared by dissolving the toxicant in an organicliquid such as acetone, methylene chloride, chlorobenzene and petroleumdistillates. The preferred organic solvent carriers are those which areadapted to accomplish the penetration and impregnation of the pestenvironment and particularly soil with the toxicant compounds and are ofsuch volatility as to leave little permanent residue thereon.Particularly desirable carriers are the petroleum distillates boilingalmost entirely under 400 F. at atmospheric pressure and having a flashpoint of about F.

In further embodiments, the toxicants as employed in accordance with thepresent invention, or compositions containing the same, can beadvantageously employed in the present invention in combination with oneor more pesticidal or preservative compound. In such embodiment, suchpesticidal or preservative compound is employed either as a supplementaltoxicant, an additament or as an adjuvant. Representative pesticidalcompounds include:

Dithiocarbamate compounds, such as ferbam(tris[dimethyldithiocarbamato]iron), maneb([ethylenebis(dithiocarbamato) ]manganese mancozeb(the coordinationproduct of zinc ion and manganese ethylenebisdithiocarbamate),nabam(disodium ethylenebis[dithiocarbamate]), thiram(bis[dimethylthiocarbamoyl1disulfide), zineb([ethylenebis(dithiocarbamato) ]zinc), ziram(bis[dimethyldithiocarbamato]zinc Other Common Named Fungicides, such ascaptan (N- [(trichloromethyl)thio] -4-cyclohexenel ,Z-dicarboximidechloranil (tetrachloro-para-benzoquinone dichlone(2,3-dichloro-l,4-naphthoquinone), glyodin (2- heptadecyl-Z-imidazolineacetate), binapacryl (2-secbutyl-4,6-dinitrophenyl3-methyl-2-butenoate), dodine (n-dodecylguanidine acetate), folpet (N-[trichloromethylthioe[phthalimide);

Quaternary Ammonium compounds, such as dialkyl dimethylammoniumchloride, alkyl dimethyl benzyl ammonium chloride;

Anilides, such as 2,3-dihydro-5-carboxanilide-6-methyll ,4- oxathiin,2,3-dihydro-5-carboxanilide-6-methyl-1,4-oxathiin-4,4-dioxide,halogenated salicylanilides such as tribrominated salicylanilides,trifluoromethyl salicylanilide;

Azines, such as 4-methyl-2,3,5,l0-tetrahydro-3,5,lO-dioxonapthalino-(2,3-b)- l ,4-thiazine;

Azoles, such as 2-mercaptobenzothiazole, 3-

trichloromethyl-S-ethoxy-l ,2,4-thiadiazole;

Quinones, such as 2,3-dinitro-l ,4-dithia-anthraquinone;

Uracils, such as o-aza-uracil;

Organosulfur compounds;

Organometallic compounds, such as phenylmercuricacetate, phenylmercuricoleate, phenylmercuric propionate, chloromethoxy acetoxy mercuripropane,bistributyl tin oxide, bis-tripropyl tin oxide, copperpentachlorophenate, copper 8-hydroxyquinolate, mercuric chloride, sodiumborate, ethylmercuric chloride; Miscellaneous other compounds, such as3,5-dimethyltetrahydro-l ,3 ,5,ZH-thiadiazine-Z-thione, dodecylpyridinium chloride, 9-undecylenic acid, l0,lO'-oxybisphenoxarsine andtetrachloroisophthalonitrile.

It is to be understood that changes and variations may be made withoutdeparting from the spirit and scope of this invention as defined by theappended claims.

I claim:

where n is an integer from 1 to 2 inclusive; x is or the integer l; Rand R may be the same or different, and are selected from the groupconsisting of phenyl, benzyl, tolyl, methoxyphenyl, halophenyl andhalobenzyl; R is selected from the group consisting of hydrogen, C Calkyl and halogen and a carrier therefor.

2. A composition consisting essentially of a compound as defined inclaim 1 wherein R and R are the same or different and are selected fromphenyl and tolyl, and R is methyl and a carrier therefor.

3. A composition consisting essentially of a compound as defined inclaim 1 which is cis or trans-l-(phenylthio-S-tosylimino)-2-(phenylsulfinyDethylehe and a carrier therefor.

4. A compound as defined in claim 1 which is cis or trans-l-(p-tolylthio-S-tosylimino)-2-(p tolylsulfonyl)ethylene and a carriertherefor.

5. A composition as defined in claim 1 additionally containing asurfactant.

6. A method for controlling fungi and bacteria which comprises applyingbiocidally effective amounts of a cis or trans compound of the formulaof SC n R where n is an integer from 1 to 2 inclusive; x is 0 or theinteger l; R and R may be the same or different, and are selected fromthe group consisting of phenyl, benzyl, tolyl, methoxyphenyl, halophenyland halobenzyl; R is selected from the group consisting of hydrogen, C-C, alkyl and halogen directly in contact with said organism.

7. The method of claim 6 wherein the compound is contacted with thefungi and bacteria by first applying it to a locus to be protected.

8. A composition for killing algae consisting essentially of a cis ortrans compound of the formula where n is an integer from 1 to 2inclusive; x is 0 or the integer 1; R and R may be the same ordifferent, and are selected from the group consisting of phenyl, benzyl,tolyl, methoxyphenyl, halophenyl and halobenzyl; R is selected from thegroup consisting of hydrogen, C -C alkyl and halogen and acarrier-therefor.

9. A method for controlling algae which comprises applying biocidallyeffective amounts of a cis or trans compound of the formula of where nis an integer from 1 to 2 inclusive; x is O or the integer 1; R and Rmay be the same or different, and are selected from the grou consistinof phenyhRlgenzyll tolylffmethogt- 15 se ecte rom t e group consistingof hydrogen, C -C alkyl and halogen directly in contact with saidorganism.

2. A composition consisting essentially of a compound as defined inclaim 1 wherein R and R'' are the same or different and are selectedfrom phenyl and tolyl, and R2 is methyl and a carrier therefor.
 3. Acomposition consisting essentially of a compound as defined in claim 1which is cis ortrans-1-(phenylthio-S-tosylimino)-2-(phenylsulfinyl)ethylene and acarrier therefor.
 4. A compound as defined in claim 1 which is cis ortrans-1-(p-tolylthio-S-tosylimino)-2-(p-tolylsulfonyl)ethylene and acarrier therefor.
 5. A composition as defined in claim 1 additionallycontaining a surfactant.
 6. A method for controlling fungi and bacteriawhich comprises applying biocidally effective amounts of a cis or transcompound of the formula of where n is an integer from 1 to 2 inclusive;x is 0 or the integer 1; R and R'' may be the same or different, and areselected from the group consisting of phenyl, benzyl, tolyl,methoxyphenyl, halophenyl and halobenzyl; R2 is selected from the groupconsisting of hydrogen, C1-C6 alkyl and halogen directly in contact withsaid organism.
 7. The method of claim 6 wherein the compound iscontacted with the fungi and bacteria by first applying it to a locus tobe protected.
 8. A composition for killing algae consisting essentiallyof a cis or trans compound of the formula where n is an integer from 1to 2 inclusive; x is 0 or the integer 1; R and R'' may be the same ordifferent, and are selected from the group consisting of phenyl, benzyl,tolyl, methoxyphenyl, halophenyl and halobenzyl; R2 is selected from thegroup consisting of hydrogen, C1-C6 alkyl and halogen and a carriertherefor.
 9. A method for controlling algae which comprises applyingbiocidally effective amounts of a cis or trans compound of the formulaof where n is an integer from 1 to 2 inclusive; x is 0 or the integer 1;R and R'' may be the same or different, and are selected from the groupconsisting of phenyl, benzyl, tolyl, methoxyphenyl, halophenyl andhalobenzyl; R2 is selected from the group consisting of hydrogen, C1-C6alkyl and halogen directly in contact with said organism.